Metal-Ligand Cooperative Approaches in Homogeneous Catalysis Using Transition Metal Complex Catalysts of Redox Noninnocent Ligands

Catalysis offers a straightforward route to prepare various value-added molecules starting from readily available raw materials. The catalytic reactions mostly involve multi-electron transformations. Hence, compared to the inexpensive and readily...

Carbonylation of olefins by carbon monoxide and alcohols in the presence of Pd-complex catalytic system

In order to develop new, efficient and environmentally friendly methods for the preparation of practically valuable esters of carboxylic acids, studies of the hydroalkoxycarbonylation reaction of a number of terminal olefins of normal structure (hexene-1, heptene-1, octene-1, nonene-1) with carbon monoxide and alcohols in presence of metal complex catalysts based on palladium phosphine complexes at low carbon monoxide pressures (≤ 20 atm).Two-and three-component systems based on PdCl2 and Pd(Acac)2, PdCl2(PPh3)2, Pd(PPh3)4 complexes containing a free ligand (PPh3) as a stabilizer and Bronsted acid (TsOH) as a promoter were studied as catalysts. It was shown that only the three-component systems PdCl2-PPh3-TsOH, PdCl2(PPh3)2-PPh3-TsOH, Pd(Acac)2-PPh3-TsOH, and Pd(PPh3)2-PPh3-TsOH have the highest catalytic activity in the studied reactions. It was found that the reaction of hydroalkoxycarbonylation of α-olefins proceeds with the formation of a mixture of linear and branched products. The influence of various conditions of the reaction (the ratio of the initial reagents and the components of the catalytic systems, temperature, CO pressure, duration) on the course of the process and on the yield of the target products was investigated. The optimal parameters of the studied reactions have been found.

Recent Advances in Homogeneous Catalysis via Metal–Ligand Cooperation Involving Aromatization and Dearomatization

Recently, an increasing number of metal complex catalysts have been developed to achieve the activation or transformation of substrates based on cooperation between the metal atom and its ligands. In such “cooperative catalysis,” the ligand not only is bound to the metal, where it exerts steric and electronic effects, but also functionally varies its structure during the elementary processes of the catalytic reaction. In this review article, we focus on metal–ligand cooperation involving aromatization and dearomatization of the ligand, thus introducing the newest developments and examples of homogeneous catalytic reactions.

Aqueous electrocatalytic CO2 reduction using metal complexes dispersed in polymer ion gels

The polymer ion gel support can improve electrocatalytic CO2 reduction using metal complex catalysts in water.

Strategies and mechanisms of metal–ligand cooperativity in first-row transition metal complex catalysts

The use of metal–ligand cooperation (MLC) by transition metal bifunctional catalysts has emerged at the forefront of homogeneous catalysis science.

Screening of metal complex catalysts using bidentate Schiff base ligands for controlled cationic polymerization of vinyl ethers using in situ complexation method

Appropriate ligand scaffolds in cationic polymerization were screened using various bidentate Schiff base ligand/ZrCl4 initiating systems.